Linear Laser-induced Fluorescence Research Articles

Cam-based vibration-counter-balanced laser-induced fluorescence scanner for multiplexed capillary detection

Laser-induced fluorescence (LIF) rotary scanners have been successfully used for multiplexed capillary detection. However, these scanners have a limitation that the capillaries have to be assembled in a circular format, which can be inconvenient for certain applications. A linear LIF scanner works well for flat parallel capillary arrays, but motor accelerations/decelerations (for direction changes) and scanning head vibrations introduce high instrumental noises. The number of capillaries that can be scanned by a linear scanner is limited because of the above constraints. We have constructed a cam-based scanner in an attempt to address these issues. A cam-based scanner eliminates the motor accelerations/decelerations but not the scanning head vibrations. In this work, we attach a second scanning head to the cam on the opposite side of the first scanning head to counter-balance the mechanical vibrations. With this modification, we improve the limit of detection by more than 3 times (from 69 pM to 20 pM fluorescein). We also increase the capillary number capacity by more than 6 times; the total number of capillaries that can be scanned is 426 if 150-μm-o.d. capillaries are used or 320 if 200-μm-o.d. capillaries are used. To demonstrate the utility of this instrument, we assemble a 99-capillary array on one capillary holder and perform capillary electrophoresis of two fluorescent dyes; separations in all capillaries are successfully monitored simultaneously. We also apply it for detecting fluorescently labeled proteins resolved by 24 s-dimension capillaries in a chip-capillary hybrid device; two-dimensional separation results are nicely produced.

Quantitative measurement of hydroxyl radical (OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy**Project supported by the National Natural Science Foundation of China (Grant No. 11272338), the Science and Technology on Scramjet Key Laboratory Funding, China (Grant No. STSKFKT 2013004), and the China Scholarship Council.

An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence (LIF) methods is developed to quantitatively measure the concentrations of hydroxyl in CH4/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.

Dependence of laser-induced fluorescence on exciting-laser power: partial saturation and laser – plasma interaction

In recent publications on laser-induced fluorescence (LIF), the measurements are usually constricted to the region of weak exciting-laser power – the so called linear LIF. In this work, a practical formula F(E_L) = (alpha) *E_L / (1+(beta)*E_L) describing the dependence of partially saturated fluorescence on the exciting-laser power is derived, together with practical implementation suggestions and comments on its limitations. In the conclusion, the practical formula is proposed with the limitation for validity (beta)*EL = 0.4, where (alpha)*EL is the hypothetical linear fluorescence without saturation effects, and a more general formula is derived, which is valid for higher values of (alpha)*EL as well. Extending the range of exciting laser power to the region of partial saturation enhances the signal-to-noise ratio. Such measurements in a surface dielectric barrier discharge further reveal discharge disruption by photoelectrons emitted from the dielectric surface. Methods of control and solution of this problem are discussed.

Measurement of OH concentration profiles by laser diagnostics and modeling in high-pressure counterflow premixed methane/air and biogas/air flames

Detailed kinetic mechanisms validated under atmospheric or low-pressure flame conditions cannot generally be directly extrapolated toward high pressure, due to the lack of experimental data or to uncertainties concerning the rate constants of elementary reactions. It is thus necessary to complete the experimental database and to extend the validation domain of combustion mechanisms at high pressure. In this work, OH concentration profiles were measured in high-pressure methane/air and biogas/air laminar premixed counterflow flames by linear laser-induced fluorescence at different equivalence ratios (0.7–1.2) and pressures (0.1–0.7MPa). Each flame was calibrated in absolute OH concentration by a combination of laser absorption and planar laser-induced fluorescence measurements. Experimental results were compared with simulations using the OPPDIF code and three detailed kinetic mechanisms: two versions of the Gas Research Institute Mechanism, GRI-Mech 2.11 and GRI-Mech 3.0, and the recently updated GDFkin®3.0_NCN mechanisms. Results show that the flame front positions are very well predicted by modeling with the three mechanisms for lean and stoichiometric CH4/air flames and stoichiometric CH4/CO2/air flames. However, discrepancies appear at a higher equivalence ratio (Φ=1.2) for the CH4/air flames and at a lower equivalence ratio (Φ=0.7) for the CH4/CO2/air flames. OH mole fractions are quantitatively well predicted at high pressure in all cases, while systematic overestimation by modeling is observed at atmospheric pressure. A kinetic analysis of the results is also presented.

A cam-based laser-induced fluorescence scanner for capillary array electrophoresis

Capillary array electrophoresis (CAE) is an important high throughput analytical technique. Laser-induced fluorescence (LIF) has been the dominant detection method for CAE owing to its low limit of detection (LOD) and wide linear dynamic range (LDR). Linear LIF scanners were first used in CAE because linear motions of an objective match well with a common planar array of capillaries. A problem with linear scanners is that the motor is required accelerating/decelerating so that all capillaries can be properly scanned, which makes motion control complicated and reduces the duty cycle. Rotary scanners were developed to overcome this problem. While rotary scanners have been successfully applied in CAE, the capillaries have to be arranged in a circular format, which can be inconvenient in some cases. In this report, we describe a cam-based LIF scanner as an alternative technique for CAE detection. In this system, a rotary motor is mechanically linked with a capillary holder via a cam. During operation, the motor carries the cam in a rotary motion that drives an array of capillaries on the holder to move back and forth across the objective for fluorescence detection. Using this design, the capillaries can be parallel-arranged in a plane while the motor acceleration/deceleration is avoided. To demonstrate the feasibility of this approach, we constructed a prototype instrument with a constant-velocity scanning distance of ∼10 mm, a scanning frequency of 3 Hz and a duty cycle of ∼70%. The scanner exhibited a LOD of 69 pM of fluorescein and a LDR of 3.5 orders of magnitude. Multiplexed capillary SDS-PAGE was performed on this scanner for protein separations.

NO Reburn and Formation Chemistry in Methane Diffusion Flames

Abstract We have applied time-resolved picosecond linear laser-induced fluorescence to obtain spatially resolved profiles of NO in laminar methane/air and methane/nitric oxide/air counterflow diffusion flames at atmospheric pressure. Temperature profiles have been measured with broadband CARS of nitrogen. Flames at strain rates from 59 s−1 to 269 s−1 were studied to characterize the strain rate dependence of the NO concentration. The work shows that NO concentrations decrease with increasing strain rate. Comparisons have been made with predicted NO levels obtained using two different chemical kinetic mechanisms (Lindstedt and co-workers and GRI-Mech. 3.0). Computed concentrations are shown to be in good agreement with experimental data. The addition of up to 600 ppm NO to the fuel did permit an assessment of differences in the reburn chemistry between the two mechanisms.

Laser-induced fluorescence measurements and modeling of absolute CH concentrations in strained laminar methane/air diffusion flames

We have applied linear laser-induced fluorescence to obtain spatially resolved profiles of CH radicals in laminar methane/air and methane/nitric oxide/air counterflow diffusion flames at atmospheric pressure. Excitation and detection of transitions in the A–X band and calibrating the optical detection efficiency via Rayleigh scattering allowed the determination of absolute radical concentrations. Flames at strain rates from 59 to 269 s −1 were studied to characterize the strain rate dependence of the CH concentration. The work shows that CH concentrations increase with increasing strain rate. Comparisons have been made with predicted CH levels obtained using two different chemical kinetic mechanisms (Lindstedt et al. and GRI-Mech. 3.0). Computed concentrations are shown to be in good agreement with experimental data. It was furthermore found that the addition of up to 600 ppm NO to the fuel did not have a measurable effect on the CH radical concentration. This is also in agreement with predictions from both mechanisms. The current work has shown that measurements of absolute CH radical concentrations are possible in non-premixed flames without the need for spatial temperature or quenching corrections.

LIF MEASUREMENTS AND CHEMICAL KINETIC ANALYSIS OF NITRIC OXIDE FORMATION IN HIGH-PRESSURE COUNTERFLOW PARTIALLY PREMIXED AND NONPREMIXED FLAMES

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of nitric oxide concentration ([NO]) in laminar, methane/air counterflow partially premixed and nonpremixed flames at six pressures up to 15 atm using excitation near 226.03 nm in the γ(0,0) band of NO. For partially premixed flames, fuel-side equivalence ratios (φB) of 1.45, 1.6, and 2.0 are studied at a global strain rate of 20 s−1. For nonpremixed flames, a complete set of NO measurements at global strain rates of 20 s−1, 30 s−1, and 40 s−1 is presented to supplement previously reported data in such flames. The quantitative NO measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The effect of radiative heat loss on NO predictions is assessed by using a modified version of the code that considers radiation in the optically thin limit. The linear LIF measurements of [NO] are corrected for variations in the electronic quenching rate coefficient by using major species and temperature profiles generated by the opposed-flow flame code plus quenching cross sections for NO available from the literature. A pathway analysis provides the relative contribution of different NO formation mechanisms to the total amount of NO produced at various pressures. Quantitative reaction path diagrams are used to investigate pictorially species interactions during NO formation. Finally, we identify key reactions controlling NO concentrations in counterflow partially premixed and nonpremixed flames by using a sensitivity analysis. For the nonpremixed flames, NO measurements at pressures of 2–5 atm disagree substantially with predictions from either GRI mechanism. On the other hand, both mechanisms predict observed NO concentrations reasonably well beyond 6 atm. In general, for our nonpremixed flames, NO formation is dominated by the prompt route at lower pressures with an increasing contribution from the N2O pathway at higher pressures. For partially premixed flames, GRI 3.0 mimics the basic quantitative trends found in our LIF measurements at 1–15 atm. The kinetic analysis indicates that the prompt mechanism dominates at lower pressures, whereas the thermal and N2O pathways become more important at higher pressures. At any given pressure, a reduction in partial premixing results in kinetic behavior approaching that of the nonpremixed flames.

LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane–air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A–X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (ϕB) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH4 and 75% N2; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for ϕB=1.45 and ϕB=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames.

Measurements of absolute CH concentrations by cavity ring-down spectroscopy and linear laser-induced fluorescence in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure.

We report quantitative, spatially resolved measurements of methylidyne concentration ([CH]) in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure by using both cavity ring-down spectroscopy (CRDS) and linear laser-induced fluorescence (LIF) in the A-X (0, 0) band. Three partially premixed (phiB = 1.45, 1.6, 2.0) flames plus a single nonpremixed methane-air flame are investigated at a global strain rate of 20 s(-1). These quantitative measurements are compared with predictions from an opposed-flow flame code when utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The LIF measurements of [CH] are corrected for variations in the electronic quenching rate coefficient by using predicted major species concentrations and temperatures along with quenching cross sections for CH that are available in the literature. The peak CH concentration obtained by CRDS is used to calibrate the quenching-corrected LIF measurements. Excellent agreement is obtained between CH concentration profiles measured by using the CRDS and LIF techniques. The spatial location of the CH layer is very well predicted by GRI 3.0; moreover, the measured and predicted CH concentrations are in good agreement for all the flames of this study.

Spectroscopic, calibration and RET issues for linear laser-induced fluorescence measurements of nitric oxide in high-pressure diffusion flames

Two different strategies are compared for linear laser-induced fluorescence (LIF) measurements of nitric oxide concentration ([NO]) in counter-flow diffusion flames at high pressures via the A-X(0,0) system. Excitation of NO via a rovibronic transition at 226.03 nm is found to be slightly better compared to a previously utilized excitation wavelength of 225.58 nm. An indirect approach based on the computed spectral overlap fraction is verified and applied to calibrate [NO] measurements in counter-flow diffusion flames at high pressures. A five-level model for NO molecular dynamics is presented and utilized to investigate the effects of rotational energy transfer (RET) on linear LIF measurements of [NO] at pressures up to 15 atm. The results indicate that rotational relaxation effects are essentially negligible under high-pressure conditions at low laser fluences, and thus they need not be accounted for when measuring [NO] using linear LIF. The calibration technique is validated by direct comparisons to [NO] measurements made at pressures up to 5 atm via another calibration method, based on doping NO in counter-flow premixed flames at the same pressure. Using this calibration technique, LIF measurements of [NO] are obtained in a series of counter-flow diffusion flames at pressures up to 15 atm. These measurements are found to be in excellent agreement with previously reported measurements of [NO] in similar flames.

Hydroxyl radical concentration measurements near the deposition substrate in low-pressure diamond-forming flames

OH radical profiles were measured in the near-deposition-surface region in low-pressure, stagnation-flow diamond-forming flames using laser-induced fluorescence (LIF). The objective of these measurements was to explore the chemistry of the diamond chemical-vapor deposition (CVD) process by resolving the OH profile near the deposition substrate. Detailed OH LIF measurements were performed in stagnation-flow diamond-forming C 2H 2/O 2 flames with equivalence ratios of 1.80, 2.10, and 2.32. The flame with an equivalence ratio of 1.80 exhibited no diamond film growth, while the flame with an equivalence ratio of 2.32 exhibited significant diamond film growth. The LIF measurements were performed in the linear LIF regime and the laser frequency was scanned across the spectral profile of the P 1(3) line in the (1,0) band of the A 2 Σ +– X 2 Π electronic transition at each spatial location. In earlier H 2 CARS measurements, the temperature gradients near the deposition substrate were resolved and good agreement between the measured temperature profiles and the numerical modeling results was demonstrated. The measured LIF profiles were corrected for electronic quenching and the variation of the Boltzmann fraction with temperature. Major species profiles were calculated using the results of the numerical flame code. The laser beam spatial profile was accounted for by convolving the theoretical OH profiles from the numerical model with the measured laser beam profile. The experimental OH profiles for all three cases are compared with theoretical results calculated using a stagnation-flame model that includes the diamond-formation surface chemistry. The measured OH concentrations near the deposition surface are substantially lower than theoretical results from a flame model that does not include the surface chemistry, but somewhat higher than for the model that does include the diamond-formation surface chemistry, especially for the flames with equivalence ratios of 1.80 and 2.10. The measured OH profile for the flame with an equivalence ratio of 2.32 is in good agreement with the profile calculated using a theoretical model with diamond-formation surface chemistry.

QUANTITATIVE LASER-INDUCED FLUORESCENCE MEASUREMENTS AND MODELING OF NITRIC OXIDE IN HIGH-PRESSURE (6–15 ATM) COUNTERFLOW DIFFUSION FLAMES

Laser-induced fluorescence (LIF) measurements of NO concentration ([NO]) have been obtained along the centerline of methane–air counterflow diffusion flames at 6 to 15 atm. This study is an extension of our previous work involving measurements of [NO] in similar flames at two to five atm, wherein we had used a counterflow premixed flame for calibration. For the flames studied here, a method based on computed overlap fractions is developed to calibrate [NO] measurements at higher pressures. The linear LIF measurements of [NO], which are corrected for variations in the electronic quenching rate coefficient, are compared with numerical predictions from an opposed-flow flame code utilizing two Gas Research Institute (GRI) chemical kinetic mechanisms (versions 2.11 and 3.0). The effect of radiative heat loss on code predictions is accounted for by using an optically thin radiation model. The revised GRI mechanism (version 3.0) offers a significant improvement in prompt-NO predictions for these flames compared to the older version (2.11), especially at pressures below eight atm. However, a consistent discrepancy remains in the comparisons, particularly at peak NO locations for pressures lower than six atm. The measurements display a continuing trend of decreasing NO concentration with increasing pressure at 6–15 atm as expected for flames dominated by prompt NO. The discrepancy between measurements and predictions decreases with rising pressure so that the revised GRI mechanism predicts [NO] with reasonable accuracy at pressures above six atm.

Fluorescence-lifetime measurements in atmospheric-pressure flames using nanosecond-pulsed lasers

Measurements of fluorescence lifetimes are needed to quantify concentration measurements when using linear laser-induced fluorescence. However, lifetimes are only a few nanoseconds for many important species at atmospheric pressure. When using a typical Q-switched laser with a pulse width of about 10 ns, the fluorescence follows the shape of the laser pulse and the lifetime cannot be easily measured. In this paper, a technique is described for experimentally determining the fluorescence lifetime in atmospheric-pressure flames using a nanosecond-pulsed laser; that is, measurement of a lifetime an order-of-magnitude faster than the laser pulse itself. This technique relies on an observable temporal shift in the fluorescence signal as a function of the lifetime. Simulations show the efficacy of this approach, and data in liquid samples and in an atmospheric-pressure flame show excellent agreement with prior picosecond measurements. This technique is successful because only the temporal shift is examined and details of the fluorescence profile are ignored.

Laser-saturated and linear laser-induced fluorescence measurements of nitric oxide in counterflow diffusion flames under non-sooting oxygen-enriched conditions

We report quantitative, spatially resolved, laser-induced fluorescence (LIF) measurements of NO concentration ([NO]) in non-sooting, oxygen-enriched counterflow diffusion flames at atmospheric pressure. Three different flames containing 25%, 50%, and 100% CH 4 , respectively, in the fuel stream and 100%, 50%, and 35% O 2 , respectively, in the oxidizer stream are investigated at a global strain rate of 20 s m 1 . Excitation of NO is achieved at 224.45 nm in the n (0,0) band and detection is performed in a 2-nm region centered at 235.78 nm in the n (0,1) band. Excitation scans ensure no spectral background problems under the high-temperature conditions of oxygen enrichment. Detection scans obtained at the excitation wavelength verify no interferences from any other species, particularly O 2 . Quantitative axial profiles of [NO] are presented for all three flames. Linear LIF measurements are compared to laser-saturated fluorescence (LSF) measurements to assess the utility of a broadband LSF technique at temperatures approaching 3000 K. Numerical computations for all counterflow diffusion flames are conducted using OPPDIF with GRI Mech-3.0. The effect of gas-phase radiation is considered in the modeling. The results indicate excellent agreement between the measured and predicted NO concentrations for all three flames. A comparison of the linear LIF and LSF measurements also yields excellent agreement.

Spatially resolved absolute concentration and fluorescence-lifetime determination of H2CO in atmospheric-pressure CH4/air flames

Using laser-induced fluorescence (LIF), spatially resolved concentration profiles of formaldehyde (H2CO) were obtained in the preheating zone of atmospheric-pressure premixed CH4/air flames stabilized on the central slot of a multiple-slot burner similar in construction to domestic boilers. The isolated pQ1(6) rotational line (339.23 nm) in the 21 041 0 vibronic combination transition in the A1A2- \tilde{X} 1A1 electronic band system around 339 nm was excited in the linear LIF intensity regime. For a quantification of quenching effects on the measured LIF signal intensities, relative fluorescence quantum yields were determined from direct fluorescence lifetime as a function of height above the slot exit. Absolute H2CO number densities in the flames were evaluated from a calibration of measured LIF signal intensities versus those obtained in a low-pressure sample with a known H2CO vapor pressure. Peak concentrations in the slightly lean and rich flames reached (994±298) and (174±52) ppm, respectively.

In-Situ Calibration Technique for Laser-Induced Fluorescence Measurements of Nitric Oxide in High-Pressure, Direct-Injection, Swirling Spray Flames

We report spatially resolved laser-induced fluorescence (LIF) measurements of nitric oxide (NO) in a preheated, two-atmosphere, lean direct-injection (LDI) spray flame. The spray is produced by a hol-low-cone, pressure-atomized nozzle supplied with liquid heptane. NO is excited via the Q2(26.5) transition of the γ(0,0) band. Detection is performed in a 2-nm region centered on the γ (0,1) band. A complete scheme is developed by which quantitative NO concentrations in high-pressure LDI spray flames can be measured by applying linear LIF. Standard excitation and detection scans are performed to assess possible interferences and to verify a non-resonant wavelength for subtracting the influence of oxygen interferences and Mie scattering in the NO detection window. NO is doped into the reactants and convected through the flame with no apparent destruction, thus allowing an NO fluorescence calibration to be taken inside the flame environment. The in-situ calibration scheme is validated by comparisons to a reference flame. Relative axial calibration slopes are utilized in order to obtain radial profiles of absolute NO concentrations. These quantitative NO profiles are presented and analyzed so as to better understand the operation of lean-direct injectors for gas turbine combustors.

Quantitative measurements of nitric oxide in high-pressure (2–5 atm), swirl-stabilized spray flames via laser-induced fluorescence

We report spatially resolved, linear laser-induced fluorescence (LIF) measurements of nitric oxide (NO) in preheated, high-pressure (2.09 to 5.35 atm), lean direct-injection (LDI) spray flames. The spray is produced by a hollow-cone, pressure-atomized nozzle supplied with liquid heptane. NO is excited via the Q 2(26.5) transition of the γ(0, 0) band. Detection is performed in a 2-nm region centered on the γ(0, 1) band. The major goal of this study is the validation and application of a complete LIF scheme by which quantitative NO concentrations can be measured in high-pressure LDI spray flames. Standard excitation and detection scans have been performed to assess possible interferences and to validate a nonresonant wavelength so as to subtract the influence of oxygen interferences in the NO detection window. NO is doped into the reactants and convected through the flame with no apparent destruction, thus allowing an NO fluorescence calibration to be taken inside the flame environment. The in situ calibration scheme is validated by comparisons with reference flames at high pressure. Quantitative radial NO profiles are presented at 2.09, 3.18, 4.27, and 5.35 atm and analyzed so as to better understand the operation of lean-direct injectors for gas turbine combustors. Downstream NO measurements in the LDI flames indicate an overall pressure scaling corresponding to P 0.74.

Laser-induced fluorescence measurements and modeling of nitric oxide in counterflow partially premixed flames

Quantitative measurements of NO concentration ([NO]) have been obtained along the centerline of atmospheric pressure, methane–air, counterflow partially premixed flames using the laser-induced fluorescence (LIF) technique. The effect of partial premixing was studied by investigating flames with fuel-side equivalence ratios (φ B) of 1.45, 1.6, 1.8, and 2.0 at a constant global strain rate near 20 s −1. Linear LIF measurements of [NO] are corrected for variations in the electronic quenching rate coefficient by using major species profiles generated by an opposed-flow flame code and quenching cross-sections for NO available from the literature. Corrected linear LIF measurements of [NO] and temperatures measured using thin filament pyrometry are compared with numerical predictions from the opposed-flow flame code by utilizing the GRI (version 2.11) mechanism for the NO kinetics. The effect of radiative heat loss on code predictions is accounted for by using an optically thin radiation model. Reasonably good agreement exists between LIF [NO] measurements and predictions in all flames. In particular, all predictions fall within 10% of measurements at peak [NO] locations. Spatial separation was observed between regions where prompt-NO and thermal-NO dominate in the φ B = 1.45 flame. A previously modified rate coefficient for the prompt-NO initiation reaction improved agreement between predictions and measurements in the region dominated by prompt NO.

Laser-Induced Fluorescence Measurements and Modeling of Nitric Oxide in High-Pressure Counterflow Diffusion Flames

Quantitative laser-induced fluorescence (LIF) measurements of NO concentration ([NO]) have been obtained along the centerline of prompt-NO dominated, methane-air counterflow diffusion flames at two to five atm, Global strain rates of 20, 30 and 40 s−1 were investigated at each pressure, with the addition of a 15 s−1 case at three and four atm. Linear LIF measurements of [NO] are corrected for variations in the electronic quenching rate coefficient by using major species profiles generated by an opposed-flow flame code and quenching cross-sections for NO available from the literature. Corrected linear LIF measurements of [NO] are compared with numerical predictions from the opposed-flow flame code by utilizing the GRI (version 2.11) mechanism for the NO kinetics. The effect of radiative heat loss on code predictions is accounted for by using an optically thin radiation model. A modest decrease in predicted temperature owing to radiative heat loss causes a significant decrease in predicted [NO], indicating the temperature sensitivity of the prompt-NO kinetics. Comparisons between [NO] measurements and predictions show that the GRI mechanism underpredicts prompt-NO by a factor of two to three at all pressures. The underprediction peaks at 2 to 3 atm, and decreases with pressure from 3 to 5 atm. Although the GRI mechanism does not display this trend, predictions with a modified rate coefficient for the prompt-NO initiation reaction give qualitative agreement with the experimentally observed variation. However, modifying the prompt-NO initiation reaction is not sufficient to account for the differences between measurements and predictions, thus indicating a need for refinement of the CH chemistry.